Europâisches Patenta mt

19 European Patent Office @ Publication number : 0 044 874 Office européen des brevets B1

EUROPEAN PATENT SPECIFICATION

(45) Date of publication of patent spécification : % int. ci.3 : C 09 D 5/1 4, C 09 D 5/1 6 03.08.83 (21) Application number: 81900328.6 (22) Date of filing : 30.01.81 (86) International application number : PCT/JP 81/00021 (87) International publication number : WO WO/81021 (06.08.81 Gazettee 81/19)

(g) STABLE ANTI-FOULING PAINT COMPOSITION.

(30) Priority : 31.01.80 JP 11188/80 (73) Proprietor : Yoshitomi Pharmaceutical Industries, . 22.03.80 JP 36486/80 Ltd. 35 Hlranomachi 3-chome Higashi-ku (43) Date of publication of application : Osaka-shi Osaka 541 (JP) 03.02.82 Bulletin 82/05 (72) Inventor : SUENOBU, Koreyoshi (45) Publication of the grant of the patent : 850, Oaza-Yoshiki Buzen-shi 03.08.83 Bulletin 83/31 Fukuoka 828 (JP) Inventor : HIDAKA, Yasuhiro (84) Designated contracting states : 2-37-3, Makizukadai Sakal-shi DE FR GB NL SE Osaka 590-01 (JP) Inventor : IKE, Tetsuji 97-1, Oaza-Naoe Yoshitomi-machi cited Chikujogun (56) Références : Fukuoka 871 (JP) GB A 2 018 260 JP A 54 119 534 (74) Représentative : von Kreisler, Alek, Dipl.-Chem. et al Deichmannhaus am Hauptbahnhof D-5000 Kôln 1 (DE)

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o o Note : Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shali be f iled in CL a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) LU European patent convention). Jouve, 18, rue St-Denis, 75001 Paris, France This invention relates to a stabilized antifouling paint composition. More particularly, it relates to an antifouling paint composition stabilized against viscosity increase and gelation during storage, which comprises a triorganotin-containing polymer, cuprous oxide and a stabilizer. So far, paints containing cuprous oxide as an active antifouling ingredient have been used for preventing such marine organisms as the barnacle and sea lettuce from sticking to ship hulls and various marine constructions. As such paints, there have been used vinyl resin antifouling paints (continuous contact paints) and rosin type antifouling paints (soluble matrix paints). However, the initial rate of dissolution of the copper ion is so great with them that the antifouling effect cannot be maintained for long. They are also problematic with regard to resistance to alkalis, drying behavior, film strength and so forth, and consequently are not satisfying antifouling paints. To overcome these disadvantages, triorganotin compounds such as triphenyltin salts and tributyltin salts have been employed. Recently, triorganotin-containing polymers which are salts from triorganotin oxides or hydroxides or halides and such high-molecular-weight compounds as various carboxyl- containing acrylic or alkyd resins have become the objects of attention as antifoulants superior to said simple triorganotin salts. Antifouling paints containing the triorganotin-containing polymers as antifouling ingredients can maintain their antifoulant performance over a prolonged period of time at minimum and constant rates of dissolution or leaching of the active ingredients. They are epoch-making paints which also have an increased safety in coating with them and bring about a reduction in fuel costs. Supposedly, the superior characteristics of these triorganotin-containing polymers consist in that they are slowly hydrolyzed in sea water and the release of the active ingredients, namely triorganotin components, is thereby controlled. While the triorganotin-containing polymers may be used alone, they are usually used in combination with inorganic copper compounds so as to attain constant antifouling effects. However, when cuprous oxide is combinedly used with the triorganotin-containing polymers to prepare antifouling paints, the paints are subject to changes during storage, which lead to viscosity increase and eventually to gelation. To solve this problem, attemps have been made, such as the two-component system in which cuprous oxide and a triorganotin-containing polymer are mixed just prior to coating therewith (e. g. Japanese Patent Application laid open (Kokai) under N°. 119, 534/1979) and the use of expensive and highly toxic copper rhodanide in place of cuprous oxide (e. g. Japanese Patent Applications laid open under NOO. 50, 236/1978 and 125, 233/1979). However, none are satisfactory. As a result of intensive research by the present inventors on the method of stabilizing antifouling paints containing as active ingredients cuprous oxide, which has so far been used and is safer and inexpensive, and a triorganotin-containing polymer for storage for a prolonged period, it has now been found that such antifouling paints can be stabilized against viscosity increase and gelation by the addition of a small but effective amount of a hindered phenol. This finding has led to the present invention. Thus, the invention provides an antifouling paint composition stabilized against viscosity increase and gelation, which comprises a triorganotin-containing polymer and cuprous oxide as combined active ingredients, a stabilizing amount of a hindered phenol, and a solvent therefor. The triorganotin-containing polymer, which is the active ingredient to be used in the practice of the present invention, includes homopolymers of a triorganotin salt of an unsaturated carboxylic acid such as acrylic, methacrylic, maleic or itaconic acid, copolymers thereof with each other or with a copolymeriz- able unsaturated compound such as vinyl chloride, vinyl acetate, vinylidene chloride, alkyl acrylate or methacrylate, styrene or vinyltoluene, or a mixture thereof, and further triorganotin salts of a high-acid- value carboxyl-containing alkyd or acrylic resin. Preferred are copolymers of tributyltin or triphenyltin methacrylate and methyl methacrylate as well as copolymers of tributyltin or triphenyltin methacrylate, methyl methacrylate and an alkyl acrylate such as methyl, ethyl, butyl or 2-ethylhexyl acrylate. The antifouling paint composition of the present invention may contain, in addition to the above- mentioned triorganotin-containing polymer, a resin such as natural resin, chlorinated rubber, chlorinated polyethylene, vinyl copolymer resin or epoxy resin, for increasing film strength or controlling viscosity or for improving dispersibility of cuprous oxide, which is another active ingredient. The composition may also contain any other conventional paint ingredients, such as extenders, pigments and plasticizers, unless these react with the stabilizing agent in accordance with the present invention and adversely affect the paint performance. The amount of each paint ingredient can be selected depending upon the pigment volume concentration, antifoulant performance and other factors. The hindered phenol, which is the stabilizing agent in accordance with the present invention, includes those phenolic compounds that have at least one tertiary alkyl group or an equivalent thereto ortho to the hydroxyl group. Preferred examples are 2,6-di-tert-butylphenol, 2,6-ditert-butyl-alpha- dimerthylamino-p-cresol, tert-butythydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di.tert.amylhydro- quinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butyl- phenol). Other examples are 2.6-di-tert-butyt-p-cresot, 2,4-dimethyl-6-tert-butylphenol, butylated hydroxy- anisole, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetra- kis(3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)methane, octadecyl 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6- tris(3,5-di-tert-butylbenzyl)benzene, and 2,2'-methylenebis(6-(1-methylcyclohexyl)-p-cresol). The amount of the stabilizing agent is not critical. However, in view of formulations generally employed, antifoulant performance, economy and other factors, the stabilizing agent is used, for example, in an amount of 0.1- 3 % by weight, preferably 0.5-1 % by weight, based on the whole paint composition. The active ingredients (the triorganotin-containing polymer and cuprous oxide) are used in an antifouling amount. And the ratio of the triorganotin-containing polymer and cuprous oxide can be selected referring to known combined paint composition of this kind. Aliphatic and aromatic hydrocarbons such as heptane, toluene and xylene, and mixtures thereof may serve as the solvents. Some ketones, esters and halogenated hydrocarbons may also be used. The following examples will illustrate the present invention in more detail.

Example 1

Polymer Preparation

350 g of tributylin methacrylate and 150 g of methyl methacrylate were dissolved in 500 g of xylene, and then 2.5 g of benzoyl peroxide was added as a polymerization initiator. Polymerization was carried out at 90-110 °C for 10 hours, to give a slightly yellow, viscous, 50 % copolymer solution in xylene. The weight average molecular weight of the copolymer as measured by gel permeation chromatography was 83,000.

Example 2

Polymer Preparation

325 g of tributyltin methacrylate, 125 g of methyl methacrylate and 50 g of butyl acrylate were dissolved in 500 g of xylene, 2.5 g of benzoyl peroxide was added as a polymerization initiator, and polymerization was effected at 80-100 °C for 8 hours to give a slightly yellow, viscous, 50 % copolymer solution in xylene. The weight average molecular weight of the copolymer as measured by gel permeation chromatography was 75,000.

Example 3

Polymer Preparation

250 g of tributyltin methacrylate, 200 g of methyl methacrylate and 50 g of 2-ethylhexyl acrylate were dissolved in 500 g of xylene, 2.5 g of alpha,alpha'-azobisisobutyronitrile was added as a polymerization initiator, and polymerization was effected at 80-85 °C for 4 hours to give a slightly yellow, viscous, 50 % copolymer solution in xylene. The weight average molecular weight of the copolymer as measured by gel permeation chromatography was 55,000.

Example 4

Paint Preparation

The 50% tributyltin-containing-polymer solution in xylene as prepared in each of Examples 1-3 was mixed with other paint ingredients in accordance with the following recipe in a ball mill to prepare a standard test paint. Standard Test Paint Composition :

Example 5

Storage Stability Test

The standard test paints A, B and C prepared in Example 4 were tested for storage stability with and without the addition of 0.5 % by weight of a stabilizing agent, namely 2,6-di-tert-butylphenol, 2.6-di-tert- butyl-alpha-dimethylamino-p-cresol, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert- amylhydroquinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) or 2,2'-methyienebis(4-ethyi-6-tert- butylphenol). For carrying out the test in an accelerated manner, the test paints were each placed in a tightly stoppered 500-ml bottle and stored in a thermostat maintained at 50 °C for a month, while observing the paints for their condition at intervals. Without addition of any stabilizing agent, Paints A, B and C each showed a significant viscosity increase after storage for 3 days and complete gelation after storage for 10-12 days. To the contrary, Paints A, B and C stabilized by the addition of any of the stabilizing agents mentioned above maintained their good condition throughout the 30-day storage period. The stabilizing agent to be added in accordance with the present invention may also be used in combination with such an organic phosphorus compound as triphenyl phosphite and/or such an organic sulfur compound as dilauryl thiodipropionate.

1. An antifouling paint composition stabilized against viscosity increase and gelation during storage which comprises a triorganotin-containing polymer and cuprous oxide as combined active ingredients, a stabilizing amount of a hindered phenol, and a solvent therefor. 2. The composition of Claim 1, wherein said triorganotin-containing polymer is a copolymer of tributyltin methacrylate and methyl methacrylate. 3. The composition of Claim 1, wherein said triorganotin-containing polymer is a copolymer of tributyltin methacrylate, methyl methacrylate and an alkyl acrylate. 4. The composition of Claim 3, wherein said alkyl acrylate is butyl acrylate. 5. The composition of Claim 3, wherein said alkyl acrylate is 2-ethylhexyl acrylate. 6. The composition of any of the preceding claims, wherein said hindered phenol is selected from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-alpha-dimethyl-amino-p-cresol, tert-butylhydroquinone, 2,5-di- tert-butyl-hydroquinone, 2,5-di-tert-amyihydroquinone, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-8-tert-butylphenol).

1. Antifouling-Anstrichmittel, das gegen Viskositätszunahme und Gelbildung während der Lagerung stabilisiert ist, dadurch gekennzeichnet, daß es ein triorganozinnhaltiges Polymerisat und Kupfer(I)-oxid als kombinierte aktive Bestandteile, eine stabilisierende Menge eines behinderten Phenols und ein Lösungsmittel hierfür enthält. 2. Anstrichmittel nach Anspruch 1, dadurch gekennzeichnet, daß das triorganozinn-haltige Polyme- risat ein Copolymerisat aus Tributylzinnmethacrylat und Methylmethacrylat ist. 3. Anstrichmittel nach Anspruch 1, dadurch gekennzeichnet, daß das triorganozinn-haltige Polyme- risat ein Copolymerisat aus Tributylzinnmethacrylat, methylmethacrylat und einem Alkylacrylat ist. 4. Anstrichmittel nach Anspruch 3, dadurch gekennzeichnet, daß das Alkylacrylat Butylacrylat ist. 5. Anstrichmittel nach Anspruch 3, dadurch gekennzeichnet, daß das Alkylacrylat 2-Ethylhexylacry- lat ist. 6. Anstrichmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das behinderte Phenol ausgewählt ist aus 2,6-Di-tert-butylphenol, 2,6-Di-tert-butyl-alpha-dimethylamino-p- cresol, tert-Butylhydrochinon, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon, 2,2'-Methylen- bls(4-methyl-6-tert-butyl-phenol) und 2,2'-Methylen-bis(4-ethyl-6-tert-butylphenol).

1. Une composition de peinture anti-fouling stabilisée contre l'augmentation de viscosité et la gélification durant le stockage, caractérisée en ce qu'elle comprend un polymère contenant un triorganoétain et de l'oxyde cuivreux en tant qu'ingrédients actifs combinés, une quantité stabilisatrice d'un phénol empêché, et un solvant pour la composition. 2. Composition selon la revendication 1, caractérisée en ce que le polymère contenant un triorganoétain est un copolymère de méthacrylate de tributylétain et de méthacrylate de méthyle. 3. Composition selon la revendication 1, caractérisée en ce que le copolymère de triorganoétain est un copolymère de méthacrylate de tributylétain, de méthacrylate de méthyle et d'un acrylate d'alcoyle. 4. Composition selon la revendication 3, caractérisée en ce que ledit acrylate d'alcoyle est l'acrylate de butyle. 5. Composition selon la revendication 3, caractérisée en ce que ledit acrylate d'alcoyle est l'acrylate de 2-éthylhexyle. 6. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que ledit phénol empêché est choisi parmi le 2,6-di-tert-butylphénol, le 2,6-di-tert-butyl-alpha-diméthyl-amino-p- crésol, la tert-butylhydroquinone, la 2,5-di-tert-butyl-hydroquinone, la 2,5-di-tert-amylhydroquinone, le 2,2'-méthylène-bis (4-méthyl-6-tert-butylphénol) et le 2,2'-méthylène-bis(4-éthyl-6-tert-butylphénol).